Hindawi Publishing Corporation

Chinese Journal of Engineering

Volume 2013, Article ID 362682, 14 pages
http://dx.doi.org/10.1155/2013/362682

Research Article
Numerical Simulation and Investigation of System Parameters
of Sonochemical Process

Sankar Chakma and Vijayanand S. Moholkar

Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781 039, Assam, India

Correspondence should be addressed to Sankar Chakma; sankar@iitg.ernet.in

Received 25 July 2013; Accepted 19 August 2013

Academic Editors: B.-Y. Cao, S. Tang, and G. Xiao

Copyright © 2013 S. Chakma and V. S. Moholkar. This is an open access article distributed under the Creative Commons
Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is
properly cited.

This paper presents the effects of various parameters that significantly affect the cavitation. In this study, three types of liquid
mediums with different physicochemical properties were considered as the cavitation medium. The effects of various operating
parameters such as temperature, pressure, initial bubble radius, dissolved gas content and so forth, were investigated in detail. The
simulation results of cavitation bubble dynamics model showed a very interesting link among these parameters for production of
oxidizing species. The formation of ∙ OH radical and H2 O2 is considered as the results of main effects of sonochemical process.
Simulation results of radial motion of cavitation bubble dynamics revealed that bubble with small initial radius gives higher
sonochemical effects. This is due to the bubble with small radius can undergo many acoustic cycles before reaching its critical
radius when it collapses and produces higher temperature and pressure inside the bubble. On the other hand, due to the low surface
tension and high vapor pressure, organic solvents are not suitable for sonochemical reactions.

1. Introduction undergoes an implosive/energetic collapse resulting in either

The sonochemistry concept is a well-established technique,
and now it is considered as one of the most popular advanced
oxidation processes. In the last few decades, sonochemical
process became one of the most popular techniques for
synthesis of catalysts as well as different types of materials
[4–7], degradation of pollutants [8–12], synthesis of biodiesel
[13, 14], and so forth. Numerous literatures on sonochemistry
have already been published [15–18] which reported the
various beneficial effects of sonochemistry. The principal
phenomenon behind all of these effects is the cavitation.
Cavitation is nothing but nucleation, growth, and implosive
collapse of a bubble. Cavitation occurs through the forma-
tion of bubbles or cavities present in liquid medium. Each
cavitating bubble contains gas or vapor or a mixture of
gas-vapor. When bubble contains only gas, the expansion
of bubble is mainly by diffusion, pressure reduction, or by
rise in temperature. However, there are several parameters
which are directly involved in transient cavitation. Transient
cavitation is nothing but the growth of bubbles extensively
over time scales of the order of the acoustic cycle and then
fragmentation, decaying oscillation, or a repeat performance
[19]. Cavitation can also be the result of the enlargement of
cavities that are already present in bulk liquid. Sometimes
cavitation bubbles are suspended/trapped in tinny cracks in
the interface of solid and liquid. These cavitation bubbles
grow and collapse in the medium based on the pressure
variation inside the bubble. On the basis of pressure variation,
cavitation can be categorized into four subsections: (1)
hydrodynamic cavitation, (2) acoustic cavitation, (3) optic
cavitation, and (4) particle cavitation [20]. Hydrodynamic
cavitation is the result of pressure variation in the liquid
medium due to the flow variation of liquid through the
medium, while acoustic cavitation is due to the passing of
acoustic waves in the liquid medium. Generally, acoustic
cavitation occurs in the frequency range of 20 kHz to 1 MHz,
that is, high power low frequency [20]. In acoustic cavitation,
very high temperature and pressure (∼ 5000 K and ∼ 500 bar)
are produced inside the bubbles due to transient collapse of
cavitation bubbles. The bubble collapse occurs within as small
time as 50 ns, and it is almost adiabatic. During the collapse
of the bubble, many species are formed such as H2 , O2 , H2 O2 ,
2 Chinese Journal of Engineering
O3 , ∙ OH, ∙ H, ∙ O, and HO2 ∙ . Among these species ∙ OH radical
is the most predominant radical species [21, 22] having an
oxidizing potential of 2.33 V [9, 23]. For greater details in
cavitation concepts, we would like to refer the readers to see
the state of art reviews by Xu et al. [4], Apfel [24], Gong and
Hart [25], Suslick et al. [26], and Gogate and Pandit [27].
2. Cavitation Bubble Dynamics Model
In order to investigate the various effects of cavitation, we
have considered a model for a single cavitation bubble to
simulate the radial motion of cavitation bubble. Although the
single bubble analysis for radial motion of cavitation bubble
does not give the entire phenomenon of the sonochemical
process, but it can give a qualitative physical insight into the
mechanism. The resultant effect of sonochemical reaction is
the collective oscillations and collapse of cavitation bubbles,
with strong interaction between them. For simulation of
radial motion, the single bubble model is the most popular
model to present the effects of cavitation, namely, physi-
cal and chemical effect. The physical and chemical effects
induced by ultrasound and cavitation bubbles in the system
can be determined using diffusion limited ordinary differen-
tial equation (ODE) model. This model is basically based on
the boundary layer approximation proposed by Toegel et al.
[28]. This radial motion of cavitation bubble model is derived
from the partial differential equation (PDE) model of Storey
and Szeri [29], which showed that water vapor entrapment in
the cavitation bubble is mainly a diffusion limited process and
not the condensation limited process. The main components
of the radial motion of cavitation bubble dynamics are: (1)
Keller-Miksis equation for the radial motion of the bubble
[30], (2) equation for the diffusive flux of water vapor and
heat conduction through bubble wall. The overall diffusion
coefficient in ternary mixture (e.g. N2 –O2 –H2 O in case of
air bubbles) or binary mixture (e.g., N2 –H2 O or O2 –H2 O
or Ar–H2 O) has been determined using Blanc’s law [31], (3)
equation for heat conduction through cavitation bubble wall,
and (4) overall energy balance treating the cavitation bubble
as an open system. The set of 4 ODEs are also given below.
(1) Radial motion of the cavitation bubble:
𝑑𝑅/𝑑𝑡 𝑑2 𝑅 3 𝑑𝑅/𝑑𝑡 𝑑𝑅 2
(1 − ) 𝑅 2 + (1 − )( )
𝑐L 𝑑𝑡 2 3𝑐L 𝑑𝑡
1 𝑑𝑅/𝑑𝑡
= (1 + ) (𝑃𝑖 − 𝑃𝑡 ) (1)
𝜌L 𝑐L
𝑅 𝑑𝑃𝑖 𝑑𝑅/𝑑𝑡 2𝜎
+ − 4] − .
𝜌L 𝑐L 𝑑𝑡 𝑅 𝜌L 𝑅
Internal pressure in the bubble: 𝑃𝑖 = 𝑁tot (𝑡)𝑘𝑇/
[4𝜋(𝑅3 (𝑡) − ℎ3 )/3].
Pressure in bulk liquid medium: 𝑃𝑡 = 𝑃0 − 𝑃A
sin(2𝜋𝑓𝑡).
(2) Diffusive flux of water molecules: 𝑑𝑁W /𝑑𝑡 = 4𝜋𝑅2
𝐷W (𝜕𝐶W /𝜕𝑟)|𝑟=𝑅 ≈ 4𝜋𝑅2 𝐷W ((𝐶W,𝑅 − 𝐶W )/𝑙diff ).
Instantaneous diffusive penetration depth:
𝑙diff = min(√(𝑅𝐷w )/|𝑑𝑅/𝑑𝑡| , 𝑅/𝜋).
(3) Heat conduction across bubble wall: 𝑑𝑄/𝑑𝑡 = 4𝜋𝑅2 𝜆
(𝜕𝑇/𝜕𝑟)|𝑟=𝑅 ≈ 4𝜋𝑅2 𝜆((𝑇0 − 𝑇)/𝑙th ).
Thermal diffusion length: 𝑙th = min
(√𝑅𝜅/|𝑑𝑅/𝑑𝑡|, 𝑅/𝜋).
(4) Overall energy balance: 𝐶𝑉,mix 𝑑𝑇/𝑑𝑡 = 𝑑𝑄/𝑑𝑡−𝑃𝑖 𝑑𝑉/
𝑑𝑡 + (ℎW − 𝑈W )𝑑𝑁W /𝑑𝑡.
Mixture heat capacity: 𝐶𝑉,mix = ∑ 𝐶𝑉,𝑖 𝑁𝑖
(where, 𝑖 = N2 /O2 /H2 O).
Molecular properties of water: Enthalpy: ℎw =
4𝑘𝑇𝑜 .
Internal energy: 𝑈W = 𝑁W 𝑘𝑇(3 + ∑3𝑖=1 ((𝜃𝑖 /𝑇)/
(exp(𝜃𝑖 /𝑇) − 1))).
Heat capacity of various species (𝑖 = N2 /O2 /
H2 O):
2
𝑓𝑖 (𝜃 /𝑇) exp (𝜃𝑖 /𝑇)
𝐶𝑉,𝑖 = 𝑁𝑖 𝑘 ( + ∑( 𝑖 2
)) . (2)
2 (exp (𝜃𝑖 /𝑇) − 1)
The initial conditions of the ordinary differential equa-
tions are taken as: at 𝑡 = 0, 𝑅 = 𝑅𝑜 , 𝑑𝑅/𝑑𝑡 = 0, 𝑁w =
0, 𝑄 = 0, and 𝑇 = 𝑇𝑜 . Thermodynamic data for various
species and physicochemical properties of various solvents,
that is, cavitation medium, are given in Tables 1 and 2.
The thermal conductivity and diffusion coefficient (transport
parameters for the heat and mass transfer) are estimated
using Chapman-Enskog theory using Lennard-Jones 12-6
potential at the bulk temperature of the liquid medium [1–
3, 31]. This model ignores the diffusion of gas across bubble
interface, because the time scale for the diffusion of gases
is much higher than the time scale of cavitation bubble
model. The ODEs in the bubble dynamics model have been
solved simultaneously using Runge-Kutta 4th- and 5th-order
adaptive step size method [32]. Various parameters used in
the numerical solution of radial motion of cavitation bubble
dynamics and their numerical values are given in Tables 1 and
2. The other parameters are as follows: ultrasound frequency
(𝑓) = 20 kHz, ultrasound pressure amplitude (𝑃A ) = 150 kPa,
initial bubble radius (𝑅𝑜 ) = 5 𝜇m, sound velocity in water
(𝑐W ) = 1481 m/s, sound velocity in toluene (𝑐T ) = 1275 m/s,
and sound velocity in n-hexane (𝑐H ) = 1203 m/s. All these
parameters remain unchanged unless otherwise stated.
Physical Effect of Ultrasound. Ultrasound propagates through
the medium in the form of longitudinal wave with series
of compression and rarefaction and causes rapid oscillatory
motion of fluid elements called microstreaming. This motion
gives rise to intense micromixing in the medium. The
magnitude of the microstreaming velocity is given by 𝑢 =
𝑃A /𝜌𝑐. Substituting values of 𝑃A as 1.5 × 105 Pa (or 1.5 bar),
𝜌w = 1000 kg/m3 , and 𝑐w = 1481 m/s gives 𝑢w = 0.101 m/s.
Sonochemical Effect of Cavitation Bubbles. The numerical
solution of bubble dynamics model predicts the temperature,
Chinese Journal of Engineering
Table 1: Thermodynamic data for various species (data taken from [1–3]).
Degrees of freedom Lennard-Jones force constants
Species
(translational + rotational) (𝑓𝑖 ) 𝜎 (10−10 m)
N2 5 3.68
O2 5 3.43
Ar 3 3.42
H2 O 6 2.65
C6 H12 6 5.75
C6 H5 –CH3 6 5.82
Table 2: Physicochemical properties of various solvents as cavitation medium.
Solvent Boiling point (K) Density (kg/m3 )
Water 373 1000
Toluene 384 867
n-Hexane 341 658
#: calculated using Antoine type correlations.
pressure, and the number of gas and solvent molecules
in the bubble at transient collapse. At transient collapse,
temperature and pressure reach extreme conditions, which
result in dissociation of molecules to form various chemical
species. To calculate the composition of the bubble at the
time of collapse, we assume that thermodynamic equilibrium
is attained [9]. The equilibrium mole fraction of different
chemical species in the bubble at the peak conditions reached
at transient collapse is estimated using Gibbs free-energy
minimization technique [33]. The radial motion of cavitation
bubbles generates intense convection in the medium through
two phenomena.
(i) Microconvection [20]: 𝑉turb (𝑟, 𝑡) = (𝑅2 /𝑟2 )(𝑑𝑅/𝑑𝑡).
(ii) Shock (or acoustic) waves [34, 35]: 𝑃AW (𝑟, 𝑡) = (𝜌L /
4𝜋𝑟)(𝑑2 𝑉𝑏 /𝑑𝑡2 ) = 𝜌L (𝑅/𝑟)[2(𝑑𝑅/𝑑𝑡)2 + 𝑅(𝑑2 𝑅/ 𝑑𝑡2 )],
where 𝑉𝑏 is the volume of the bubble. A representative value
of 𝑟 is taken as 1 mm. In bubble dynamic model, direct
estimation of initial bubble radius is very difficult. Several
phenomena such as rectified diffusion and fragmentation of
the bubble cause continuous change in this parameter. In
a multibubble system, a large variation in this parameter
may be expected. In order to investigate the influence of this
parameter, two numerical values for this parameter, namely, 5
and 10 𝜇m, are selected for this present study. The equilibrium
composition of the bubble contents was determined using
the FactSage online software [36], which is based on the
free-energy minimization algorithm same as proposed by
Eriksson [33].
3. Numerical Solution of Mathematical Model
The simulation results of radial motion of cavitation bubble
dynamics are depicted in Figures 1, 2, 3, 4, and 5 and Tables
3, 4, 5, 6, and 7. Tables 3–7 present the temperature (𝑇max )
and pressure (𝑃max ) peaks reached at the moment of transient
collapse of cavitation bubble, the number of water molecules
in the bubble at collapse, and the equilibrium composition of
3
Characteristic vibrational temperatures 𝜃 (K)
𝜀/𝑘 (K)
92 3350
113 2273
124 —
380 2295, 5255, 5400
386.4 1036, 1932, 1987, 2104, 4193
451 1004, 1056, 2112, 2153, 2326, 4224, 4375
Viscosity (Pa-s) Surface tension (N/m) Vapor pressure# (kPa)
1.0 × 10−6 0.072 2.5
6.8 × 10−7 0.029 4.0
5.0 × 10−7 0.018 16.2
the various species resulting from dissociation of entrapped
molecules in the bubble when the temperature and pressure
reached to its extreme conditions during transient collapse of
cavitation bubbles.
3.1. Initial Bubble Size in the Liquid Medium. Bubbles with
different initial radius present in the liquid medium play an
important role in cavitation. Kumar and Moholkar [37] have
reported that the smaller bubble has higher Laplace pressure,
which results in higher expansion and more intense collapse
during the transient collapse. In this present study, a single
bubble model with different initial radius has been chosen to
present the effects of bubble radius in sonochemical process.
From Table 3, it could be seen that the ∙ OH radical formation
during transient collapse of cavitation bubble is higher with
the initial bubble radius of 5 𝜇m followed by 25 𝜇m. This
is due to the bubble with small bubble radius can undergo
many acoustic cycles before reaching its critical radius when
it collapses, and as a result the highest temperature peak is
reached at the moment of transient collapse of the cavitation
bubble with 5 𝜇m radius bubble as shown in Figure 1 and
Table 3.
3.2. Static Pressure of the System. As stated earlier in the
previous section, the cavitation is nothing but the nucle-
ation, growth, and implosive collapse of bubbles, but the
growth/expansion of the bubble depends on the system’s
static pressure. So, when the bubble contains vapor, cavitation
may occur due to reduced static pressure sufficiently at
constant temperature. To investigate the effects of pressure,
five different static pressures ranging from 100–300 kPa have
been chosen. The results showed that as the static pressure
increases the radical formation decreases drastically; even it
becomes zero at higher ambient static pressure. This is due
to at elevated static pressure, the sonochemical effects get
eliminated which directly affects the generation of radical
formation, provided the applied pressure must be greater
than or equal to the acoustic pressure amplitude (𝑃𝑜 ≥ 𝑃AW )
[9, 38]. The highest ∙ OH radical production was seen at nearly
4 Chinese Journal of Engineering

6 6

Radius (R/Ro )
Radius (R/Ro )
3 3

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(a)
6000 3000
Temperature (K)

Temperature (K)
3000 1500

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(b)
11
6 · 1012
No. of water vapor

1 · 10

No. of water vapor

molecules

molecules
5 · 1010 3 · 1012

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(c)
4
1 · 10 1500
Pressure (bar)

Pressure (bar)

5000 750

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(d)
Oscillatory velocity (m/s)

Oscillatory velocity (m/s)

0.5 10

−0.25 0

−1 −10
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(e)
300 100
amplitude (bar)
amplitude (bar)

Acoustic wave
Acoustic wave

148 50

−4 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
5 𝜇m bubble 25 𝜇m bubble
(f)

Figure 1: Simulations of radial motion of 5 and 25 micron air bubble in water. 𝑓 = 20 kHz; 𝑃A = 150 kPa; and 𝑃𝑜 = 100 kPa. Time history
of (a) radius of the bubble; (b) temperature inside the bubble; (c) water vapor evaporation in the bubble; (d) pressure inside the bubble; (e)
microturbulence generated by the bubble; and (f) acoustic waves emitted by the bubble.
Chinese Journal of Engineering 5

6 3

Radius (R/Ro )
Radius (R/Ro )
3 1.5

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(a)
4000 1000

Temperature (K)
Temperature (K)

2000 500

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(b)
10
4 · 10 1 · 1010

No. of water vapor

No. of water vapor

molecules
molecules

2 · 1010 5 · 109

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(c)
4000 60
Pressure (bar)

Pressure (bar)

2000 30

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(d)
Oscillatory velocity (m/s)
Oscillatory velocity (m/s)

0.1

−0.1 0

−0.4 −0.1
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(e)
60 1.5
amplitude (bar)
amplitude (bar)

Acoustic wave
Acoustic wave

30 0.75

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles

120 kPa 150 kPa

(f)

Figure 2: Simulations of radial motion of 5 micron air bubble in water at 120 kPa and 150 kPa. 𝑓 = 20 kHz; 𝑃A = 150 kPa; and 𝑅𝑜 = 5 𝜇m.
Time history of (a) radius of the bubble; (b) temperature inside the bubble; (c) water vapor evaporation in the bubble; (d) pressure inside the
bubble; (e) microturbulence generated by the bubble; and (f) acoustic waves emitted by the bubble.
6 Chinese Journal of Engineering

6 10

Radius (R/Ro )

Radius (R/Ro )
3 5

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(a)
6000 3000
Temperature (K)

Temperature (K)
3000 1500

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(b)
10
2 · 1012

No. of water vapor

3 · 10
No. of water vapor

molecules
molecules

1.5 · 1010 1 · 1012

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(c)
4
1 · 10 2000
Pressure (bar)

Pressure (bar)

5000 1000

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(d)
Oscillatory velocity (m/s)
Oscillatory velocity (m/s)

0.5 1

0 −0.5

−0.5 −2
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(e)
300 60
amplitude (bar)
amplitude (bar)

Acoustic wave
Acoustic wave

150 30

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles

283 K 343 K
(f)

Figure 3: Simulations of radial motion of 5 micron air bubble in water at 283 K and 343 K. 𝑓 = 20 kHz; 𝑃A = 150 kPa; and 𝑃𝑜 = 100 kPa.
Time history of (a) radius of the bubble; (b) temperature inside the bubble; (c) water vapor evaporation in the bubble; (d) pressure inside the
bubble; (e) microturbulence generated by the bubble; and (f) acoustic waves emitted by the bubble.
Chinese Journal of Engineering 7

6 6

Radius (R/Ro )

Radius (R/Ro )
3 3

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(a)
6000 6000
Temperature (K)

Temperature (K)
3000 3000

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(b)
11

No. of water vapor

1 · 1011
No. of water vapor

1 · 10

molecules
molecules

5 · 1010 5 · 1010

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(c)
4
1 · 10 1 · 104
Pressure (bar)

Pressure (bar)

5000 5000

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(d)
Oscillatory velocity (m/s)

Oscillatory velocity (m/s)

0.5 0.5

−0.25 −0.25

−1 −1
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(e)
400 300
amplitude (bar)

amplitude (bar)
Acoustic wave

Acoustic wave

200 150

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles

Oxygen bubble Nitrogen bubble

(f)

Figure 4: Simulations of radial motion of 5 micron air bubble in water with O2 bubble and N2 bubble. 𝑓 = 20 kHz; 𝑃A = 150 kPa; and
𝑃𝑜 = 100 kPa. Time history of (a) radius of the bubble; (b) temperature inside the bubble; (c) water vapor evaporation in the bubble; (d)
pressure inside the bubble; (e) microturbulence generated by the bubble; and (f) acoustic waves emitted by the bubble.
8 Chinese Journal of Engineering

4 6

Radius (R/Ro )

Radius (R/R o)
2 3

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(a)
6000 1500

Temperature (K)
Temperature (K)

3000 750

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(b)

2 · 105 3 · 1011
vap. molecules
No. of toluene

vap. molecules
1 · 105 No. of hexane 1.5 · 1011

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(c)
4
1 · 10 1000
Pressure (bar)

Pressure (bar)

5000 500

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(d)
Oscillatory velocity (m/s)
Oscillatory velocity (m/s)

0.005

−0.1 −0.0025

−0.3 −0.01
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles
(e)
400 2
amplitude (bar)
amplitude (bar)

Acoustic wave
Acoustic wave

200 1

0 0
0 1 2 3 4 5 0 1 2 3 4 5
No. of acoustic cycles No. of acoustic cycles

Toluene n-hexane
(f)

Figure 5: Simulations of radial motion of 5 micron air bubble in toluene and n-hexane as cavitation medium. 𝑓 = 35 kHz; 𝑃A = 150 kPa;
and 𝑃𝑜 = 100 kPa. Time history of (a) radius of the bubble; (b) temperature inside the bubble; (c) water vapor evaporation in the bubble; (d)
pressure inside the bubble; (e) microturbulence generated by the bubble; and (f) acoustic waves emitted by the bubble.
Chinese Journal of Engineering 9

Table 3: Simulation summary of initial bubble size (𝑅𝑜 ) dependent sonochemical process.

Conditions at the first collapse of the bubble

𝑅𝑜 = 5 𝜇m 𝑅𝑜 = 25 𝜇m 𝑅𝑜 = 50 𝜇m 𝑅𝑜 = 100 𝜇m 𝑅𝑜 = 200 𝜇m
𝑇max = 3999 K 𝑇max = 1688 K 𝑇max = 778.5 K 𝑇max = 409 K 𝑇max = 329.9 K
𝑃max = 696.7 MPa 𝑃max = 30.57 MPa 𝑃max = 2.56 MPa 𝑃max = 288 kPa 𝑃max = 136 kPa
𝑉turb = 0.36 m/s 𝑉turb = 6.11 m/s 𝑉turb = 6.2 m/s 𝑉turb = 7.95 m/s 𝑉turb = 11.2 m/s
𝑃AW = 24.04 MPa 𝑃AW = 8.80 MPa 𝑃AW = 0.63 MPa 𝑃AW = 0.27 MPa 𝑃AW = 0.35 kPa
𝑁N2 = 1.28 × 1010 𝑁N2 = 1.32 × 1012 𝑁N2 = 1.03 × 1013 𝑁N2 = 8.11 × 1013 𝑁N2 = 6.44 × 1014
𝑁O2 = 3.41 × 109 𝑁O2 = 3.51 × 1011
𝑁O2 = 2.73 × 10 12
𝑁O2 = 2.16 × 1013 𝑁O2 = 1.71 × 1014
𝑁W = 2.91 × 109 𝑁W = 2.5 × 1011 𝑁W = 9.08 × 1011 𝑁W = 2.98 × 1012 𝑁W = 1.15 × 1013
Equilibrium composition of species in the bubble at collapse
Species
5 𝜇m 25 𝜇m 50 𝜇m 100 𝜇m 200 𝜇m
N2 6.26 × 10−1 6.86 × 10−1 7.38 × 10−1 7.68 × 10−1 7.79 × 10−1
O2 1.28 × 10−1 1.82 × 10−1 1.96 × 10−1 2.04 × 10−1 2.07 × 10−1
H2 O 1.41 × 10−2 1.30 × 10 −1
6.50 × 10 −2
2.80 × 10−2 1.40 × 10−2
N 1.56 × 10−5 — — — —
O 5.95 × 10−3 — — — —
H 2.83 × 10−4 — — — —
O3 1.70 × 10−5 — — — —
H2 2.53 × 10−4 — — — —
OH 9.51 × 10−3 9.03 × 10−5 — — —
HO2 5.59 × 10−4 5.81 × 10−6 — — —
H2 O2 2.00 × 10−5 — — — —
NO 8.47 × 10−2 2.58 × 10−3 1.49 × 10−6 — —
NO2 1.70 × 10−3 1.27 × 10−4 2.84 × 10−6 — —
N2 O 3.61 × 10−4 2.18 × 10 −6
— — —
NH 1.70 × 10−6 — — — —
HNO 5.95 × 10−5 — — — —
HNO2 1.75 × 10−4 7.06 × 10−6 — — —

Note: solvent = water, temperature (𝑇) = 303 K, static pressure (𝑃0 ) = 100 kPa, dissolved gas = air, and frequency (𝑓) = 20 kHz.

ambient static pressure (i.e., 100 kPa), and the production
of ∙ OH radical decreases as the static pressure approaches
to the magnitude of acoustic pressure, that is, 150 kPa. The
production of ∙ OH radical at 100 kPa is typically 1.5 fold
higher than the ∙ OH radical production at 120 kPa, while at
150 kPa or higher static pressure no ∙ OH radical formation
was seen. This result can be attributed to the temperature peak
reached at the moment of collapse of the bubble. At the time
of transient collapse, the highest temperature peak (3999 K)
was seen when the pressure was 100 kPa, while the lowest
temperature peak (∼313 K) was observed with elevated static
pressure of 300 kPa.
3.3. System Operating Temperature. Another important fac-
tor that affects the transient cavitation is system temperature.
To study the temperature effect on sonochemical process,
the numerical simulations were run in the temperature range
from 283 to 373 K (viz. 283, 303, 323, 343, and 373 K). The sim-
ulation results are depicted in Figure 3. As the temperature
in the system increases the formation of oxidizing species
due to transient cavitation of bubbles reduces drastically. This
could be attributed to the effects of bubble radius as discussed
in the earlier section. In this case, vapor bubbles grow
with increasing the temperature through the phenomenon
of boiling [20]. So, the lower the temperature means the
higher the cavitation effects in the system. Table 5 shows that
the production of ∙ OH radical is highest with the lowest
temperature, that is, at 283 K, while at the boiling point of
water no ∙ OH radical formation has been observed. The
overall trend of the ∙ OH radical production under various
operating temperature is 283 K > 303 K > 323 K > 343 K.
3.4. Type of Dissolved Gas Content. The type of dissolved
gas has an impact on bubble nucleation rate as described in
the literatures [15, 37]. The simulation results for four gases
are shown in Table 6 and Figure 4. The production of ∙ OH
radical as well as H2 O2 is highest for O2 bubble followed by
air, Ar, and N2 bubble. Also the generation of O3 per bubble
for oxygen bubble is one order of magnitude higher than
the O3 generation by air bubble. The radicals by air bubble
are formed through the reactions (3)–(22), while (24) and
(25) represent the radical formation by O2 bubble [39]. The
production of radicals is least with N2 bubble as compared to
other gas bubbles. This is due to the scavenging of radicals by
N2 molecules through the reactions (3)–(16). Moreover, there
is no regeneration of ∙ OH and O∙ radicals by O2 when the
10 Chinese Journal of Engineering

Table 4: Simulation summary of sonochemical process under various static pressures (𝑃𝑜 ).

Conditions at the first collapse of the bubble

𝑃𝑜 = 100 kPa 𝑃𝑜 = 120 kPa 𝑃𝑜 = 150 kPa 𝑃𝑜 = 200 kPa 𝑃𝑜 = 300 kPa
𝑇max = 3999 K 𝑇max = 3024 K 𝑇max = 977.3 K 𝑇max = 353.4 K 𝑇max = 312.7 K
𝑃max = 696.7 MPa 𝑃max = 286.3 MPa 𝑃max = 4.62 MPa 𝑃max = 416 kPa 𝑃max = 477 kPa
𝑉turb = 0.36 m/s 𝑉turb = 0.21 m/s 𝑉turb = 0.07 m/s 𝑉turb = 0.008 m/s 𝑉turb = 0.002 m/s
𝑃AW = 24.04 MPa 𝑃AW = 5.43 MPa 𝑃AW = 120 kPa 𝑃AW = 2 kPa 𝑃AW = 0.6 kPa
𝑁N2 = 1.28 × 1010 𝑁N2 = 1.48 × 1010 𝑁N2 = 1.78 × 1010 𝑁N2 = 2.28 × 1010 𝑁N2 = 3.28 × 1010
𝑁O2 = 3.41 × 109 𝑁O2 = 3.95 × 10 9
𝑁O2 = 4.74 × 10 9
𝑁O2 = 6.07 × 109 𝑁O2 = 8.73 × 109
𝑁W = 2.91 × 109 𝑁W = 1.81 × 10 9
𝑁W = 8.86 × 10 8
𝑁W = 8.19 × 1010 𝑁W = 3.81 × 108
Equilibrium composition of species in the bubble at collapse
Species
1 bar 1.2 bar 1.5 bar 2 bar 3 bar
N2 6.26 × 10−1 6.99 × 10−1 7.60 × 10−1 7.68 × 10−1 7.83 × 10−1
O2 1.28 × 10−1 1.67 × 10−1 2.02 × 10−1 2.04 × 10−1 2.08 × 10−1
H2 O 1.41 × 10−2 7.45 × 10 −2
3.80 × 10 −2
2.80 × 10−2 9.00 × 10−3
N 1.56 × 10−5 — — — —
O 5.95 × 10−3 9.35 × 10−4 — — —
H 2.83 × 10−4 4.09 × 10−5 — — —
O3 1.70 × 10−5 3.71 × 10 −6
— — —
H2 2.53 × 10−4 1.67 × 10−4 — — —
OH 9.51 × 10−3 6.33 × 10−3 — — —
HO2 5.59 × 10−4 3.60 × 10−4 — — —
H2 O2 2.00 × 10−5 2.74 × 10−5 — — —
NO 8.47 × 10−2 4.30 × 10−2 2.64 × 10−5 — —
NO2 1.70 × 10−3 1.03 × 10−3 1.09 × 10−5 — —
N2 O 3.61 × 10−4 1.10 × 10 −4
— — —
NH 1.70 × 10−6 — — — —
HNO 5.95 × 10−5 1.38 × 10 −5
— — —
HNO2 1.75 × 10−4 1.40 × 10−4 — — —
Note: solvent = water, dissolved gas = air, initial bubble size (𝑅0 ) = 5 𝜇m, temperature (𝑇) = 303 K, and frequency (𝑓) = 20 kHz.

bubble contents are N2 gas. So the total number of radicals NH2 + O∙ 󴀘󴀯 H∙ + HNO (13)
per bubble in N2 bubbling is always lower than the other gas
bubbles. The trend of production of ∙ OH radical per bubble HNO + O∙ 󴀘󴀯 NH + O2 (14)
with various gases bubbling is as follows O2 > Air > Ar > N2 .
HNO + O∙ 󴀘󴀯 NO + ∙ OH (15)

N2 + O∙ 󴀘󴀯 N∙ + NO (3) HNO + ∙ OH 󴀘󴀯 NO + H2 O (16)

N2 + ∙ OH 󴀘󴀯 N2 H + O∙ (4) N + O2 󴀘󴀯 NO + O∙ (17)

N2 + ∙ OH 󴀘󴀯 N2 O + H∙ (5) NO + O2 󴀘󴀯 NO2 + O∙ (18)

N2 + ∙ OH 󴀘󴀯 NH + NO (6) NH + O2 󴀘󴀯 HNO + O∙ (19)

N2 + H∙ 󴀘󴀯 N2 H (7) NH + O2 󴀘󴀯 NO + ∙ OH (20)

N2 + H∙ 󴀘󴀯 NH + N∙ (8) N2 + O2 󴀘󴀯 N2 O + O∙ (21)

N + ∙ OH 󴀘󴀯 NO + H∙ (9) H∙ + O2 󴀘󴀯 HO2 ∙ (22)

∙
N2 O + O∙ 󴀘󴀯 2NO (10) OH +O2 󴀘󴀯 HO2 ∙ + O∙ (23)

NO + ∙ OH 󴀘󴀯 NO2 (11) O∙ + O 2 → O 3 (24)

NH + ∙ OH 󴀘󴀯 NH2 + O∙ (12) 2HO2 ∙ 󴀘󴀯 H2 O2 + O2 (25)

Chinese Journal of Engineering 11

Table 5: Simulation summary of system temperature (𝑇𝑜 ) dependent sonochemical process.

System temperature
𝑇 = 283 K 𝑇 = 303 K 𝑇 = 323 K 𝑇 = 343 K 𝑇 = 373 K
Conditions at the first collapse of the bubble
𝑇max = 3989 K 𝑇max = 3999 K 𝑇max = 3733 K 𝑇max = 2683 K 𝑇max = 811.7 K
𝑃max = 681.5 MPa 𝑃max = 696.7 MPa 𝑃max = 623.9 MPa 𝑃max = 175.3 MPa 𝑃max = 1.79 MPa
𝑉turb = 0.35 m/s 𝑉turb = 0.36 m/s 𝑉turb = 0.45 m/s 𝑉turb = 1.08 m/s 𝑉turb = 4.63 m/s
𝑃AW = 24.75 MPa 𝑃AW = 24.04 MPa 𝑃AW = 21.56 MPa 𝑃AW = 4.43 MPa 𝑃AW = 220 kPa
𝑁N2 = 1.38 × 1010 𝑁N2 = 1.28 × 1010 𝑁N2 = 1.21 × 1010 𝑁N2 = 1.13 × 1010 𝑁N2 = 1.04 × 1010
𝑁O2 = 3.66 × 109 𝑁O2 = 3.41 × 10 9
𝑁O2 = 3.20 × 10 9
𝑁O2 = 3.02 × 109 𝑁O2 = 2.77 × 109
𝑁W = 7.94 × 108 𝑁W = 2.91 × 109 𝑁W = 1.23 × 1010 𝑁W = 8.15 × 1010 𝑁W = 1.79 × 1012
Equilibrium composition of species in the bubble at collapse
Species
283 K 303 K 323 K 343 K 373 K
N2 7.07 × 10−1 6.26 × 10−1 4.13 × 10−1 1.16 × 10−1 6.00 × 10−3
O2 1.45 × 10−1 1.28 × 10−1 8.84 × 10−2 2.83 × 10−2 2.00 × 10−3
H2 O 1.63 × 10−2 1.41 × 10 −2
1.21 × 10 −2
2.80 × 10−2 9.93 × 10−1
N 1.72 × 10−5 1.56 × 10−5 3.84 × 10−6 — —
O 6.67 × 10−3 5.95 × 10 −3
2.44 × 10−3 5.69 × 10−5 —
H 3.21 × 10−4 2.83 × 10−4 1.06 × 10−4 2.57 × 10−6 —
O3 1.89 × 10−5 1.70 × 10 −5
8.38 × 10 −6
2.28 × 10−7 —
H2 2.91 × 10−4 2.53 × 10 −4
1.30 × 10 −4
2.29 × 10−5 —
OH 1.08 × 10−2 9.51 × 10 −3
5.27 × 10 −3
8.08 × 10−4 —
HO2 6.31 × 10−4 5.59 × 10 −4
3.25 × 10 −4
4.22 × 10−5 —
H2 O2 2.28 × 10−5 2.00 × 10 −5
1.36 × 10 −5
4.60 × 10−6 —
NO 9.51 × 10−2 8.47 × 10 −2
4.72 × 10 −2
4.57 × 10−3 —
NO2 1.90 × 10−3 1.70 × 10−3 1.04 × 10−3 1.11 × 10−4 —
N2 O 4.01 × 10−4 3.61 × 10 −4
1.88 × 10 −4
8.69 × 10−6 —
NH 1.89 × 10−6 1.70 × 10 −6
— — —
HNO 6.67 × 10−5 5.95 × 10−5 2.74 × 10−5 9.69 × 10−7 —
HNO2 1.96 × 10−4 1.75 × 10−4 1.12 × 10−4 1.76 × 10−5 —
Note: solvent = water, dissolved gas = air, initial bubble size (𝑅0 ) = 5 𝜇m, static pressure (𝑃0 ) = 100 kPa, and frequency (𝑓) = 20 kHz.

3.5. Type of Solvent or Cavitation Medium. The solvent or
cavitation medium is another important factor that affects
directly on the sonochemical process. In order to assess the
suitability of solvent for cavitation, we have chosen three
solvents with different physicochemical properties, namely,
water, toluene, and n-hexane, as shown in Table 2. To address
this issue, we have presented the numerical solution with
various solvent as cavitation medium in Figure 5 and Table 7,
which lists the temperature and pressure peak reached at the
moment of collapse with various equilibrium compositions
of species. The number of ∙ OH radical production is highest
when water is used as cavitation medium. This can be
attributed to the lower surface tension and higher vapor
pressure of the organic solvent. The production of ∙ OH
radical in water is typically two orders of magnitude higher
than that in toluene. So, due to the low intensity of bubble
collapse, organic solvents are not able to generate sufficient
numbers of radical in-situ for sonochemical reactions.
4. Conclusions
The lower is the system temperature the higher is the
cavitation effects, that is, when the system temperature is
moderately low the effect of cavitation is more. In this present
study, the radical formation due to cavitation is highest when
the system temperature is 283 K. So, the system with low
operating temperature and cavitation medium contents with
small initial bubble radius is always preferable for sono-
chemical reactions since this type of sonochemical reaction
systems are able to generate large amount of highly oxidizing
species. Due to the high vapor pressure and low surface
tension, organic solvents cannot produce large amount of
radicals in the reaction medium; thus, they are not suitable
for sonochemical reactions. However, they could be good
solvents for extraction or other processes using ultrasound.
Moreover, depending on the process requirement one can
choose the system with different gas bubbling and aqueous
or organic solvents for conducting experiments.
Nomenclature
𝐶𝑉,𝑖 : Heat capacity at constant volume, J
kg−1 K−1
𝑐L : Velocity of sound in liquid medium, m s−1
𝑐W : Velocity of sound in water, m s−1
12 Chinese Journal of Engineering

Table 6: Effect of dissolved gas content on sonochemical process.

Conditions at the first collapse of the bubble

Air bubble Nitrogen bubble Oxygen bubble Argon bubble
𝑇max = 3999 K 𝑇max = 4379 K 𝑇max = 4155 K 𝑇max = 4551 K
𝑃max = 696.7 MPa 𝑃max = 772.3 MPa 𝑃max = 758.2 MPa 𝑃max = 786.6 MPa
𝑉turb = 0.36 m/s 𝑉turb = 0.37 m/s 𝑉turb = 0.37 m/s 𝑉turb = 0.37 m/s
𝑃AW = 24.04 MPa 𝑃AW = 28.25 MPa 𝑃AW = 30.78 MPa 𝑃AW = 27.28 MPa
𝑁N2 = 1.28 × 1010 𝑁N2 = 1.63 × 1010 𝑁O2 = 1.63 × 1010 𝑁Ar = 1.63 × 1010
𝑁O2 = 3.41 × 109 𝑁W = 3.88 × 109 𝑁W = 3.88 × 109 𝑁W = 2.54 × 109
𝑁W = 2.91 × 109
Equilibrium composition of species in the bubble at collapse
Species
Air bubble Nitrogen bubble Oxygen bubble Argon bubble
N2 6.26 × 10−1 8.05 × 10−1 — —
O2 1.28 × 10−1 2.80 × 10−4 7.93 × 10−1 1.09 × 10−3
Ar — — — 8.65 × 10−1
H2 O 1.41 × 10−2 9.69 × 10−3 1.13 × 10−2 9.21 × 10−3
N 1.56 × 10−5 5.85 × 10−5 — —
O 5.95 × 10−3 5.06 × 10−4 1.87 × 10−2 1.34 × 10−3
H 2.83 × 10−4 2.48 × 10−3 2.21 × 10−4 2.59 × 10−3
−6
N3 — 1.45 × 10 — —
O3 1.70 × 10−5 — 3.28 × 10−4 —
H2 2.53 × 10−4 6.73 × 10−3 1.03 × 10−4 4.31 × 10−3
OH 9.51 × 10−3 2.50 × 10−3
1.57 × 10−2 4.09 × 10−3
HO2 5.59 × 10−4 6.77 × 10−6
2.34 × 10−3 2.07 × 10−5
H2 O2 2.00 × 10−5 8.86 × 10−7
4.75 × 10−5 1.79 × 10−6
NO 8.47 × 10−2 5.65 × 10−3
— —
NO2 1.70 × 10−3 4.93 × 10−6 — —
N2 O 3.61 × 10−4 3.02 × 10−5
— —
NH 1.70 × 10−6 2.68 × 10−5 — —
NH2 — 2.42 × 10−5 — —
NH3 — 1.78 × 10−5 — —
HNO 5.95 × 10−5 2.25 × 10−5 — —
HNO2 1.75 × 10−4 2.16 × 10−6 — —
Note: solvent = water, initial bubble size (𝑅0 ) = 5 𝜇m, temperature (𝑇) = 303 K, static pressure (𝑃0 ) = 100 kPa, and frequency (𝑓) = 20 kHz. O2 > air > Ar >
N2 .

𝑐T : Velocity of sound in toluene, m s−1 𝑁Ar : Number of Ar molecules in the bubble

𝑐H : Velocity of sound in n-hexane, m s−1 𝑁tot : Total number of molecules (gas + vapor) in
𝐷w : Diffusion coefficient of solvent vapor, m2 the bubble
s−1 𝑃𝑜 : Static pressure in the liquid medium, Pa
𝑓: Frequency of ultrasound wave, Hz 𝑃max : Pressure peak reached in the bubble at the
𝑓𝑖 : Translational and rotational degrees of time of first collapse, Pa
freedom 𝑃AW : Pressure amplitude of the acoustic wave
ℎ: Van der Waal’s hard core radius, m generated by the cavitation bubble, Pa
𝐼diff,w : Instantaneous diffusive penetration depth 𝑄: Heat conducted across bubble wall, J s−1
for water molecules 𝑅: Radius of the bubble, m
𝑘: Boltzmann constant, J K−1 𝑅𝑜 : Initial radius of the cavitation bubble, m
𝑁W : Number of water molecules trapped in the 𝑑𝑅/𝑑𝑡: Bubble wall velocity, m s−1
bubble 𝑡: Time, s
𝑁N2 : Number of N2 molecules in the bubble 𝑇: Temperature of the bubble contents, K
𝑁O2 : Number of oxygen molecules in the bubble 𝑇𝑜 : Ambient (or bulk liquid medium) temper-
𝑁T : Number of toluene molecules in the bubble ature, K
𝑁H : Number of n-hexane molecules in the 𝑇max : Temperature peak reached in the bubble at
bubble the time of first collapse, K
Chinese Journal of Engineering 13

Table 7: Simulation summary of sonochemical process with differ-

ent solvent as cavitation medium. 𝜃: Characteristic vibrational temperature(s) of
the species, K.
Conditions at the first collapse of the bubble
H2 O2 C6 H5 –CH3 C6 H12 Conflict of Interests
𝑇max = 3179 K 𝑇max = 4835 K 𝑇max = 1151 K
The authors of the paper do not have any direct financial
𝑃max = 355 MPa 𝑃max = 961.7 MPa 𝑃max = 44.55 MPa
relation that might lead to a conflict of interest for any of the
𝑉turb = 0.25 m/s 𝑉turb = 0.15 m/s 𝑉turb = 0.005 m/s authors.
𝑃AW = 12.61 MPa 𝑃AW = 30.16 MPa 𝑃AW = 188 kPa
𝑁N2 = 1.31 × 1010 𝑁N2 = 1.13 × 109 𝑁N2 = 1.07 × 1010 References
𝑁O2 = 3.47 × 109 𝑁O2 = 2.99 × 108 𝑁O2 = 2.85 × 109
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